CN103570490B - Method for gas-phase synthesis for 1,2-dichloro-3,3,4,4,5,5-hexachlorocyclopentene - Google Patents
Method for gas-phase synthesis for 1,2-dichloro-3,3,4,4,5,5-hexachlorocyclopentene Download PDFInfo
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- CN103570490B CN103570490B CN201210254955.0A CN201210254955A CN103570490B CN 103570490 B CN103570490 B CN 103570490B CN 201210254955 A CN201210254955 A CN 201210254955A CN 103570490 B CN103570490 B CN 103570490B
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- ABPBVCKGWWGZDP-UHFFFAOYSA-N FC(C(C(Cl)=C1Cl)(F)F)(C1(F)F)F Chemical compound FC(C(C(Cl)=C1Cl)(F)F)(C1(F)F)F ABPBVCKGWWGZDP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for gas-phase synthesis for 1,2-dichloro-3,3,4,4,5,5-hexachlorocyclopentene, which belongs to the field of chemical synthesis. According to the method disclosed by the invention, chromium, magnesium, zinc and aluminium are used as the active metals of a catalyst, hexachlorocyclopentene and chlorine are used as raw materials, AHF (anhydrous hydrogen fluoride) is used as a fluorinating agent, a reaction is performed in high-temperature gas-phase conditions, and the unreacted raw materials can be recycled. The catalyst selected in the method disclosed by the invention is good in stability, safe in synthesis process, and suitable for industrialized production. Due to recovery for hexachlorocyclopentene, the process is much optimized and the production cost is decreased, thus meeting the policy of low-energy-consumption and environment-friendly clean production of China.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly relate to the method for chloro-3,3,4,4,5, the 5-hexafluoro cyclopentenes of a kind of vapor-phase synthesis 1,2-bis-.
Background technology
1,2-bis-chloro-3,3,4,4,5,5-hexafluoro cyclopentenes has very high industrial value, and be a kind of broad-spectrum industrial raw material, its derived product can be used for precise electronic pcb cleaning agent, agricultural chemical insecticide, has higher using value simultaneously in the fluoride-containing PMMA synthesis such as fluorine-containing medicines intermediate.
Current 1,2-bis-chloro-3,3,4,4,5,5-hexafluoro cyclopentenes is mainly used in synthesis 1,1,2,2,3,3,4-seven fluorine pentamethylene, have been found that many Azeotrope compositions based on fluorine-containing halohydrocarbon, and use, also for diversified vapour degreasing technology as the solvent removing deflux and flux residue from printed circuit board (PCB) in some occasion.
Chloro-3,3,4,4,5, the 5-hexafluoro cyclopentenes of 1,2-bis-are as non-combustible flux, and frothing agent is used, and are also the intermediate compounds of production 1,2,3,3,4,4,5,5-octafluoro cyclopentenes.
Nineteen sixty-five American Charles F.Branauckas proposes C
5cl
xf
8-x(x=3,4,5,6,7) and HF prepare the method for chloro-3,3,4,4,5, the 5-hexafluoro cyclopentenes of 1,2-bis-under the effect of catalyzer from 150 DEG C-500 DEG C, productive rate is 37.4%.
Russian's Aleksandr Vinogradov Dmitri Wei Keduo Zorovic in 2006 research by by hexachlorocyclopentadiene and hydrogen fluoride or reaction intermediate (as C
5cl
xf
8-x(x=3,4,5,6,7)) interact obtain the method for chloro-3,3,4,4,5, the 5-hexafluoro cyclopentenes of 1,2-bis-with HF, the condition of this reaction has catalyzer-antimony chlorine compound, High Temperature High Pressure, and feature is, the reaction of initiating reagent will have catalyst S bF
ncl
5-n(n=1,2).These method severe reaction conditions or productive rate lower.
Summary of the invention
The present invention seeks to utilize simple catalyst system and applicable reaction conditions to prepare chloro-3,3,4,4,5, the 5-hexafluoro cyclopentenes of 1,2-bis-, catalyst stability is good, and building-up process safety, is suitable for suitability for industrialized production.
A kind of vapor-phase synthesis 1, 2-bis-chloro-3, 3, 4, 4, 5, the method of 5-hexafluoro cyclopentenes, it is characterized in that: by chromium, magnesium, zinc, aluminium, bismuth, titanium, the elements such as cobalt to be carried on porous support thus Kaolinite Preparation of Catalyst, pass into the mixed gas of chlorine or chlorine and rare gas element, take hexachlorocyclopentadiene as raw material, anhydrous hydrogen fluoride gas is as fluorizating agent, in Gas-phase reactor, fluoridation is there is under the high temperature gas phase of 250 DEG C-700 DEG C, generate C5Cl2F6 and by product C5ClF7, C5Cl3F5, C5Cl4F4, C5Cl5F3, C5Cl6F2, C5Cl7F, described catalyst activity metal is chromium, magnesium, zinc, aluminium, bismuth, titanium, at least one in cobalt.
Also comprise this aftertreatment and purification step in described reaction, described aftertreatment and purification step are: the mixture of fluoridation except going out after HCl and HF, then is separated 1,2-bis-chloro-3 through water distilling apparatus through washing, alkali cleaning, 3,4,4,5,5-hexafluoro cyclopentenes and by product, continue reaction after recovery.
Described porous material is gac or comprises aluminum fluoride, aluminum oxide, fluorine alumina, fluorine calcium oxide, at least one in Calcium Fluoride (Fluorspan).
Described catalyst activity metal is at least one in Mg, Cr, or the mixture of at least one in Mg, Cr and a kind of formation in Zn, Al, Bi, Ti, Co metal.
The weight ratio of described catalyzer and carrier is: 1:5-20.
The weight ratio of described catalyzer and carrier is: 1:10-15.
The duration of contact of described reaction is: 1-6s.
The duration of contact of described reaction is: 2-4s.
Wherein temperature of reaction is 300-500 DEG C.
Wherein temperature of reaction is 350-450 DEG C.
The mol ratio of described hexachlorocyclopentadiene and hydrogen fluoride and chlorine is 1:6-30:0.3-5.
The mol ratio of described hexachlorocyclopentadiene and hydrogen fluoride and chlorine is 1:10-25:1-4.
Described hexachlorocyclopentadiene is carried out gas-phase reaction by after heating and gasifying with, chlorine and anhydrous hydrogen fluoride in reactor.
Need before described reaction to activate catalyzer, described activation is that catalyzer is heated to 200 DEG C ~ 400 DEG C in N2 or other inert gas, keeps 3-5 hour; Then in the HF air-flow of HF or inert gas dilution, 1-3 hour is kept.
Described activation is for being that 30-80ml/min nitrogen passes in catalyzer by flow velocity, and catalyzer is warmed up to 200 DEG C with 10-30 DEG C/min speed and keeps 2 hours, and then is warmed up to 400 DEG C of maintenances 2 hours with 10-30 DEG C/min speed; Cool to 330 DEG C, then to pass into flow velocity be 30-60ml/min HF, and keep 2 hours at 330 DEG C.
Described Gas-phase reactor is fixed bed, shell and tube or adiabatic reactor.
The material of described reactor be nickelalloy, Hastelloy, Monel metal, because of Kang Hejin or stainless steel.
The present invention adopts gas phase process, avoids the problem of environmental pollution that liquid phase method brings, is applicable to commercial scale production; As shown in case study on implementation 1 result.
Reaction and sepn process as follows: (1) C
5cl
6with AHF(anhydrous hydrogen fluoride), Cl
2send in reaction cycle logistics with mass flowmeter and volume pump respectively, the molar ratio of three is 1:6-30:0.3-5, preferably 1:10-25:1-4.Enter in fixed-bed reactor after hybrid chamber vaporization, preheating, temperature of reaction is 250 ~ 700 DEG C, preferably 300 ~ 500 DEG C, more preferably 350-450 DEG C.Reaction pressure does not have strict restriction.AHF, Cl
2with C
5cl
6generation 1,2-dichloro hexafluoro cyclopentenes, 1,2,3-trichlorine five fluorine cyclopentenes, a small amount of chloro-2,3,3,4,4,5, the 5-seven fluorine cyclopentenes of object product 1-, HCl and above-mentioned by product is replaced carry out first addition under catalyst action after.Reaction product sends into the tripping device of HCl together with unreacted raw material; (2) the separatory method that the separation of HCl is conventional, through washing, alkali cleaning, then washes, finally carries out separatory, the incoming stock tripping device of separatory organic materials out; (3) separation of raw material adopts the distillation method known to be separated, and separates unreacted raw material C
5cl
6enter the first step reaction with above-mentioned by product circulation, above-mentioned by product all can be converted into chloro-3,3,4,4,5, the 5-hexafluoro cyclopentenes of 1,2-bis-through fluoridizing circulation.
The present invention adopts gas phase catalytic fluorination technique, carries out in fixed-bed reactor.Catalyzer carries out drying, pre-treatment before using.Pre-treatment is to obtain highly active catalyzer.
The present invention passes through the selection of catalyzer and groping of processing condition, and fluoridize through repeatedly circulating, the selectivity of final product is good, and by product is few.Production cost reduces, and method is simple, is easy to realize suitability for industrialized production.
Concrete embodiment
Below by way of the description of embodiment, the invention will be further described, but this is not limitation of the present invention, those skilled in the art are according to basic thought of the present invention, various amendment or improvement can be made, but only otherwise depart from basic thought of the present invention, all within the scope of the present invention.
Embodiment 1
20ml load is had 5%Mg, and the catalyzer of 5%Cr, 5%Zn loads fixed-bed reactor, and fixed-bed reactor open-type pipe process furnace heats.Catalyzer, under 50ml nitrogen protection, first to rise at 200 DEG C of temperature dry 2 hours with 10 DEG C/min, then; 400 DEG C of dryings 2 hours are risen to the speed of 10 DEG C/min; then, be cooled to 330 DEG C, then pass to hydrogen fluoride (HF) the gas activation catalyzer 2 hours of 50ml/min.Complete the reactivation process of catalyzer like this.
Reactor is heated to 297 DEG C, then, hexachlorocyclopentadiene is injected in the hybrid chamber of 250 DEG C with 0.22g/min by peristaltic pump, 180ml/min hydrogen fluoride and the 18ml/min chlorine through vitriol oil drying simultaneously, three kinds of raw materials enter hybrid chamber together and mix, afterwards, by reactor until surge flask, washing bottle, high alkali liquid.After experiment terminates, product is mainly distributed in surge flask and washing bottle.By the product collected through washing, after drying, carry out GC analysis.
Embodiment 2
Treat load 5%Mg, 5%Cr, after the catalyzer of 5%Al completes reactivation process, reactor is heated to 415 DEG C, then, hexachlorocyclopentadiene is injected in the hybrid chamber of 250 DEG C with 0.22g/min by peristaltic pump, 180ml/min hydrogen fluoride and the 18ml/min chlorine through vitriol oil drying simultaneously, three kinds of raw materials enter hybrid chamber together and mix, afterwards, by reactor until surge flask, washing bottle, high alkali liquid.After experiment terminates, product is mainly distributed in surge flask and washing bottle.By the product collected through washing, after drying, carry out GC analysis.
Embodiment 3
Treat load 5%Mg, 5%Cr, after the catalyzer of 5%Bi completes reactivation process, reactor is heated to 390 DEG C, then, hexachlorocyclopentadiene is injected in the hybrid chamber of 250 DEG C with 0.1g/min by peristaltic pump, 205ml/min hydrogen fluoride and the 8.2ml/min chlorine through vitriol oil drying simultaneously, three kinds of raw materials enter hybrid chamber together and mix, afterwards, by reactor until surge flask, washing bottle, high alkali liquid.After experiment terminates, product is mainly distributed in surge flask and washing bottle.By the product collected through washing, after drying, carry out GC analysis.
Embodiment 4
Treat load 5%Mg, 5%Cr, after the catalyzer of 5%Ti completes reactivation process, reactor is heated to 394 DEG C, then, hexachlorocyclopentadiene is injected in the hybrid chamber of 250 DEG C with 0.05g/min by peristaltic pump, 102.5ml/min hydrogen fluoride and the 4.1ml/min chlorine through vitriol oil drying simultaneously, three kinds of raw materials enter hybrid chamber together and mix, afterwards, by reactor until surge flask, washing bottle, high alkali liquid.After experiment terminates, product is mainly distributed in surge flask and washing bottle.By the product collected through washing, after drying, carry out GC analysis.Above-mentioned reaction result is in table 1.
C
5cl
6transformation efficiency=(C that reaction consumes
5cl
6measure/add C
5cl
6amount) × 100%
Selectivity=(summation of F6 growing amount/growing amount) × 100% of F6
Selectivity=(summation of F5 growing amount/growing amount) × 100% of F5
F6 structure is as follows:
F5 structure is as follows:
Table 1 experimental result
Claims (9)
1. a vapor-phase synthesis 1,2-bis-chloro-3,3,4, the method of 4,5,5-hexafluoro cyclopentenes, it is characterized in that: by catalyst cupport on porous support, pass into the mixed gas of chlorine or chlorine and rare gas element, be raw material with hexachlorocyclopentadiene, anhydrous hydrogen fluoride gas is as fluorizating agent, under the high temperature gas phase of 250 DEG C-700 DEG C, in Gas-phase reactor, there is fluoridation, generate C
5cl
2f
6and by product C
5clF
7, C
5cl
3f
5, C
5cl
4f
4, C
5cl
5f
3, C
5cl
6f
2, C
5cl
7f;
Described porous support is gac or comprises aluminum fluoride, aluminum oxide, fluorine alumina, fluorine calcium oxide, at least one in Calcium Fluoride (Fluorspan);
Described catalyst activity metal is the mixture of at least one in Mg, Cr and a kind of formation in Zn, Al, Bi, Ti, Co metal;
The weight ratio of described catalyzer and carrier is: 1:5-20;
The duration of contact of described reaction is: 1-6s;
The mol ratio of described hexachlorocyclopentadiene and hydrogen fluoride and chlorine is 1:6-30:0.3-5;
Need before described reaction to activate catalyzer, described activation is at N by catalyzer
2or in other inert gas, be heated to 200 DEG C ~ 400 DEG C, keep 3-5 hour; Then in the HF air-flow of HF or inert gas dilution, 1-3 hour is kept;
Described Gas-phase reactor is fixed bed or shell and tube reactor;
Also comprise this aftertreatment and purification step in described reaction, described aftertreatment and purification step are: the mixture of fluoridation except going out after HCl and HF, then is separated 1,2-bis-chloro-3 through water distilling apparatus through washing, alkali cleaning, 3,4,4,5,5-hexafluoro cyclopentenes and by product, continue reaction after recovery.
2. method according to claim 1, the weight ratio of described catalyzer and carrier is: 1:10-15.
3. method according to claim 1, the duration of contact of described reaction is: 2-4s.
4. method according to claim 1, wherein temperature of reaction is 300-500 DEG C.
5. method according to claim 4, wherein temperature of reaction is 350-450 DEG C.
6. method according to claim 1, the mol ratio of described hexachlorocyclopentadiene and hydrogen fluoride and chlorine is 1:10-25:1-4.
7. method according to claim 1, described hexachlorocyclopentadiene is carried out gas-phase reaction by after heating and gasifying with chlorine and anhydrous hydrogen fluoride in reactor.
8. method according to claim 1, described activation is for being that 30-80ml/min nitrogen passes in catalyzer by flow velocity, catalyzer is warmed up to 200 DEG C with 10-30 DEG C/min speed and keeps 2 hours, and then is warmed up to 400 DEG C of maintenances 2 hours with 10-30 DEG C/min speed; Cool to 330 DEG C, then to pass into flow velocity be 30-60ml/min HF, and keep 2 hours at 330 DEG C.
9. method according to claim 1, the material of described reactor be nickelalloy, Hastelloy, Monel metal, because of Kang Hejin or stainless steel.
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| CN105399596B (en) * | 2015-10-22 | 2017-06-16 | 北京宇极科技发展有限公司 | The method for preparing the fluorine cyclopentene isomer of trichlorine five simultaneously |
| CN105348034B (en) * | 2015-12-07 | 2018-06-01 | 天津医科大学 | A kind of method for synthesizing hexafluoro -2- butine |
| CN105884569B (en) * | 2016-04-22 | 2019-03-12 | 北京宇极科技发展有限公司 | The method for preparing 1,2- dichloro hexafluoro cyclopentene |
| CN107721810B (en) * | 2017-11-07 | 2020-12-01 | 中国民航大学 | Method for synthesizing extinguishing agent octafluorocyclobutane |
| CN111423305A (en) * | 2020-04-16 | 2020-07-17 | 北京宇极科技发展有限公司 | Separation method of five-membered cyclic fluorochloroolefin and hydrogen fluoride azeotropic mixture |
| CN111500378B (en) * | 2020-07-02 | 2020-10-30 | 北京宇极科技发展有限公司 | Cleaning agent composed of cyclic hydrochlorofluoroolefin and chain hydrochlorofluoroolefin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5180861A (en) * | 1989-10-28 | 1993-01-19 | Bayer Aktiengesellschaft | Process for the preparation of polychloro-fluoro-cyclo-pentenes |
| CN1680233A (en) * | 1997-09-17 | 2005-10-12 | 森陶硝子株式会社 | Method for producing perhalogenated cyclopentene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5180861A (en) * | 1989-10-28 | 1993-01-19 | Bayer Aktiengesellschaft | Process for the preparation of polychloro-fluoro-cyclo-pentenes |
| CN1680233A (en) * | 1997-09-17 | 2005-10-12 | 森陶硝子株式会社 | Method for producing perhalogenated cyclopentene |
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